JP4025373B2 - Method for producing carboxylic acid - Google Patents
Method for producing carboxylic acid Download PDFInfo
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- JP4025373B2 JP4025373B2 JP53732398A JP53732398A JP4025373B2 JP 4025373 B2 JP4025373 B2 JP 4025373B2 JP 53732398 A JP53732398 A JP 53732398A JP 53732398 A JP53732398 A JP 53732398A JP 4025373 B2 JP4025373 B2 JP 4025373B2
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- acid
- olefin
- branched
- catalyst
- carbon monoxide
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 15
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000003729 cation exchange resin Substances 0.000 claims description 2
- -1 poly (tetrafluoroethylene) Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000005011 phenolic resin Substances 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 19
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 6
- 229920001429 chelating resin Polymers 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、カルボン酸の製造方法に関する。本発明は、特に反応体としての一酸化炭素、及び固体酸触媒を用いたコッホ（Ｋｏｃｈ）合成による分岐カルボン酸の製造方法に関する。
今までに使用可能な方法の特徴は、固体酸触媒を魅力のないほど過酷な条件下で使用するか、固体酸触媒を腐食性ルイス酸共触媒と組み合わせるか、または固体酸触媒を非水反応系で使用するかしてはじめて、固体酸触媒を使用することにある。
特に、国際出願ＷＯ９６／２０１５４により、固体樹脂触媒を用いた非水反応系での分岐オレフィン及び一酸化炭素からのトリアルキル酢酸の製造方法が公知であり、固体樹脂触媒は、分岐オレフィン及び一酸化炭素をトリアルキル酢酸へ変換するために必要な水素を付与するのに十分な酸基を有するカチオン樹脂からなる。
該カチオン樹脂は、特に６５重量％硫酸の酸性度と少なくとも等価の酸性度を持つように規定された。
前記方法は２工程で行うことしかできず、その第１工程では、化学量論量の分岐オレフィン及び水が、所望の生成物を満足できる収率で導くことにならないことが当業者に認識される。さらに、前記方法は、２工程からなる１サイクル中に、活性水素１モル当たり１モル以上の転換オレフィンを固体触媒上で製造することができない。
一方、ＷＯ９２／１８５９２により、分岐オレフィン（特にイソブテン）及び一酸化炭素からのトリアルキル酢酸（特にピバリン酸）の製造方法が公知であり、固体酸触媒を微量のルイス酸（例えば三フッ化ホウ素）とともに使用する。
さらに、ＥＰ−Ａ−０２４９９７６からは、分岐カルボン酸の製造方法が公知であり、それは、触媒であるゼオライト（ｚｅｏｌｉｔｈ）の存在下、温度２００〜５００℃、圧力２００〜７００バールで、オレフィンを一酸化炭素及び水とともに接触転換することによる。
さらに、触媒としてペンタシル形のゼオライトを使用する。例示された実施態様によれば、高い温度（３００℃）及び圧力（３００−５００バール）のみが使用されている。
前記開示の反応条件は、安全及び環境に関する必要な対策のために高い操業コストのもとになることが理解される。
したがって、いまだ、分岐オレフィン及び一酸化炭素を出発とする分岐カルボン酸の製造方法のさらなる改善についての強い要望が存在する。
本発明の目的は、分岐カルボン酸の改善された製造方法であって、一方で、比較的緩和な条件を使用し、他方で、高転換率及び分岐酸に対して高選択率を示す方法を提供することである。広範な研究及び実験の結果、意外にもこのような目的とする改善された方法が発見された。
したがって、本発明は、一酸化炭素及び固体酸触媒を用いた反応により分岐オレフィンから分岐カルボン酸を製造する方法において、分岐オレフィン又はその前駆体を連続逆混合反応器（ｂａｃｋｍｉｘｅｄ ｒｅａｃｔｏｒ）内で反応させ、ここで、連続的に供給される一酸化炭素及び水を用いて効率的逆混合（ｂａｃｋｍｉｘｉｎｇ）を得るのに充分な供給成分及び生成物の攪拌を、分岐カルボン酸、非転換オレフィン、一酸化炭素及び水を含む流出物を抜き出しながら、前記オレフィン又はその前駆体及び一酸化炭素を分岐カルボン酸に転換するために必要な水素を付与するのに十分な酸基を有する酸性イオン交換体の存在下に行うことを特徴とする、前記製造方法に関する。
特に、本発明は、式
のトリアルキル酢酸の改善された製造方法に関する。
トリアルキル酢酸中の炭素原子の合計数は、より好ましくは５〜１９、さらに好ましくは５〜１４の範囲であり、Ｃ4−Ｃ14オレフィンに由来する。
本明細書を通して使用される用語「分岐オレフィン又はその前駆体」は、分岐オレフィン自体の他に、該特定オレフィンを容易に導くことの可能なアルコール類、エステル類又はエーテル類を本製造方法の出発材料として使用できることを意味し、これは、本方法を従来技術の方法よりも一層フレキシブルにする。
本製法によって、一般に少なくとも１個の第三炭素原子を含有するすべてのオレフィン又はその前駆体を転換することができる。
前記した連続逆混合反応器の好適な例は、連続攪拌槽型反応器（ＣＴＳＴＲ）、流動床反応器又は再循環反応器である。
前記した反応のタイプは、例えばＣｈｅｍｉｃａｌ Ｒｅａｃｔｉｏｎ Ｅｎｇｉｎｅｒｉｎｇ 第二版、Ｏ Ｌｅｖｅｎｓｐｉｅｌから公知である。
連続攪拌槽反応器又は再循環反応器が好ましい反応器である。
本発明の方法の重要な利点は、所望の分岐カルボン酸に関して、従来技術の方法に比べて高転換度及び高選択率の改善された組合せを示すとともに、比較的緩和な条件にて操作されることである。
本発明の方法にため使用する触媒は、固体酸性イオン交換体であり、容積単位触媒当たり十分量の酸活性サイト、及び、各酸サイトの強酸活性度を示す。
該触媒は、スルホン酸、リン酸又はトリハロ酢酸基を持っている樹脂からなる群から選択することができる。
好ましくは、スルホン化樹脂が用いられる。より好ましくは、樹脂がスチレンとジビニルベンゼンとのコポリマー、フェノールをベースとする樹脂、ポリ（テトラフルオロエチレン）ポリマー又はシロキサンポリマーであるスルホン化樹脂が用いられる。
活性スルホン酸基を有する好適触媒では、該樹脂は、十分な水素を提供可能なスルホン酸カチオン交換樹脂、すなわち、１活性サイト当たり少なくとも６５重量％硫酸、好ましい少なくとも７０重量％硫酸と等価な酸強度を有する樹脂を与えるように処理される。
スルホン酸基を含み、スチレン、ジビニルベンゼン及びフェノールからのコポリマーに由来し、又は（テトラフルオロエチレン）ポリマーもしくはシロキサンポリマーに由来する触媒固体樹脂が好ましい。
より好ましいものは、スチレン及びジビニルベンゼンに由来し、＞２ｍｅｑ／ｍｌ乾燥樹脂、好ましくは＞３ｍｅｑ／ｍｌ乾燥樹脂のスルホン基密度を有する触媒であるとともに、該コポリマーのジビニルベンゼン含有量は、４〜３０重量％、好ましくは８〜１８重量％である。
市販の有効な触媒の中でより好ましい特定例は、ＡＭＢＥＲＬＹＳＴ ３６又は３８、ＮＡＦＩＯＮ 又はＤＥＬＯＸＡＮ触媒である（ＡＭＢＥＲＬＹＳＴ ３６又は３８、ＮＡＦＩＯＮ及びＤＥＬＯＸＡＮは商標である）。
最も好ましいものは、ＡＭＢＥＲＬＹＳＴ ３６又は３８、ＮＡＦＩＯＮタイプの触媒である。ＣＳＴＲの反応温度は、２５℃〜２００℃の範囲にあり、好ましくは１００℃〜１５０℃の範囲にある。
反応器の圧力は、１０〜２００バール、好ましくは５０〜１００バールの範囲にある。
反応の間、所望の反応を妨害しない不活性有機溶媒、好ましくは他の反応混合物成分から容易に分離でき、かつ再循環できる溶媒を使用することができる。有機溶媒として、非極性のものを極性溶媒、例えばケトン類、エーテル、置換芳香族、エステル類及びカルボン酸と同じように使用することができる。
本製造方法のより好ましい実施態様によれば、主として製造される分岐酸は、反応器内に溶媒として存在し、そして反応器内の液体レベルを一定に維持するために、そこから水、ＣＯ、非転換オレフィン及び副生成物とともに定常的に排出される。
好ましい一実施態様によれば、ＣＳＴＲは、溶媒／触媒の重量比が０．１〜０．５ｗ／ｗ、好ましくは０．２〜０．３ｗ／ｗの溶媒及び触媒で満たされる。各成分は、連続的に反応器内に導入され、そして反応混合物が連続的に排出される。
出発オレフィンの供給量は、０．０１〜１０ｇ／ｇ／ｈｒの範囲にあるとともに、水／オレフィンのモル比は、０．５〜２モル／モル、好ましくは約１の範囲にあり、そしてＣＯ／オレフィンのモル比は、０．５〜１０００モル／モル、好ましくは１〜１００の範囲にある。
上記に特定した量を大幅に下回る水量を使用する際には、該方法は、低い選択率のために魅力的でなくなり、化学量論的（水：オレフィン＝１：１）供給物を使用するときに、選択率及び転換率が驚くほど改善されることが理解される。
本発明を、以下の実施例でさらに説明するが、これらの特定の実施態様の範囲に限定するものではない。
実施例１
５６ｇの乾燥ＡＭＢＥＲＬＹＳＴ １５を３００ｍＬのＣＳＴＲ反応器に投入し、１４５ｍＬのｎ−ヘキサン酸（溶媒）に懸濁させ、１０バールＣＯ下、ガスキャップ（ｇａｓ ｃａｐ）を定常的にパージしながら１５５℃に昇温し、続いて８０バールＣＯ流（５０ｇ／ｈｒ）の下１５５℃に１時間おくことにより活性化した。次いで、プロピレン三量体、水及びＣＯを含有する供給物（水：三量体のモル比は１：１）を、該反応器に、１１００ｒｐｍの連続攪拌のもとで８．５、１．２及び５０ｇ／ｈ（ＷＨＳＶが０．１５、０．０２１及び０．９ｇ／ｇ／ｈ）で入れ、該反応器の液体レベルを、過剰の液体生成物を除去することにより一定に保った。
これらの条件の下で、反応は、７５−８５％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して９３−９５％選択率をもって、およそ２４時間進行した。
比較例１
２０ｇのＡＭＢＥＲＬＹＳＴ １５を攪拌バッチ反応器に投入し、真空下１００℃で２時間乾燥し、５０ｇのプロパン酸（溶媒）、６ｇのプロピレン三量体３及び０．８ｇの水の溶液にに懸濁させ、最後に１５０℃へ８０バールＣＯの下で６５ｈｒ加熱した。
これらの条件の下で、反応は、９１％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して８％選択率をもって進行した。
実施例２
実施例１に記載したのと同様にして、１２０ｍＬのヘキサン酸に溶かしたＮＡＦＩＯＮ ＮＲ ５０触媒（５９ｇ）を使用して、以下の条件で、プロピレン三量体をＣＯ及び水とともに炭素数１０を含む分岐カルボン酸へ転換した。
プロピレン三量体 ８．８ｇ／ｈ（ＷＨＳＶ＝０．１６ ｇ／ｇ／ｈ）
水 １．２ｇ／ｈ（ＷＨＳＶ＝０．０２１ｇ／ｇ／ｈ）
ＣＯ ５２ ｇ／ｈ（ＷＨＳＶ＝０．９ ｇ／ｇ／ｈ）
温度 １５５℃
圧力 ８０バール
転換率は８８モル％であり、選択率は９１モル％であった。
実施例３
１３．６ｇの乾燥ＡＭＢＥＲＬＹＳＴ ３８を２４０ｍＬの攪拌オートクレーブに投入し、真空下、１５０℃で２ｈｒ乾燥し、室温まで冷却し、７４ｇのピバリン酸（溶媒）に懸濁させ、７０バールＣＯ下に加圧し、次いで１５０℃の反応温度まで昇温した。加熱期間中、２３．４ｇのＤＩＢＣ（ジ−イソブチル−カルビノール）をゆっくり連続的に該オートクレーブ内に１７時間にわたって導入した。運転の終期に反応器を冷却し、分析のために取り出した。
これらの条件の下で、反応は、１００％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して〜５６％選択率をもって進行した。
比較例２
実施例１を運転したが、ただし２０．４ｇＤＩＢＣを攪拌反応器に一度に添加（すなわちバッチ）してから７０バールＣＯに加圧し、温度を１５０℃に上げた。反応を再び１７時間行った。
これらの条件の下で、反応は、約１００％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して〜１３％選択率をもって進行した。
実施例４
実施例１を、今回、触媒としてＡＭＢＥＲＬＹＳＴ ３６を使用して運転した。触媒、供給物及び溶媒の量は約４倍小さく、すなわち、それぞれ３．１、７．４及び１９ｇであった。
これらの条件の下で、反応は、〜８５％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して〜３２％選択率をもって進行した。
比較例３
比較例２を、バッチプロセスとして４倍量の触媒、供給物及び溶媒、すなわち、それぞれ１２．１、２０．３及び７９ｇにして運転した。しかし、該供給物は、反応器を７０バールＣＯに加圧し、温度を１５０℃に上げる前に一度に添加した。
これらの条件の下で、反応は、〜９３％転換率、及び炭素数１０を有する分岐カルボン酸（ＶＥＲＳＡＴＩＣ酸 １０）に対して〜２．７％選択率をもって進行した。The present invention relates to a method for producing a carboxylic acid. The present invention particularly relates to a method for producing a branched carboxylic acid by Koch synthesis using carbon monoxide as a reactant and a solid acid catalyst.
Features of the methods that can be used to date include using solid acid catalysts under unattractive harsh conditions, combining solid acid catalysts with corrosive Lewis acid cocatalysts, or reacting solid acid catalysts with non-aqueous reactions Only when it is used in the system is the use of a solid acid catalyst.
In particular, according to international application WO 96/20154, a method for producing a trialkylacetic acid from a branched olefin and carbon monoxide in a non-aqueous reaction system using a solid resin catalyst is known, and the solid resin catalyst comprises a branched olefin and monoxide. It consists of a cationic resin having sufficient acid groups to provide the hydrogen necessary to convert carbon to trialkylacetic acid.
The cationic resin was specifically defined to have an acidity at least equivalent to an acidity of 65% by weight sulfuric acid.
Those skilled in the art will recognize that the process can only be performed in two steps, and in that first step, stoichiometric amounts of branched olefin and water will not lead to the desired product in satisfactory yield. The Furthermore, the process cannot produce more than 1 mole of converted olefin per mole of active hydrogen on a solid catalyst in one cycle consisting of two steps.
On the other hand, WO92 / 18592 discloses a method for producing a trialkylacetic acid (especially pivalic acid) from a branched olefin (especially isobutene) and carbon monoxide, and a solid acid catalyst is used as a trace amount of Lewis acid (eg boron trifluoride). Use with.
Furthermore, EP-A-0249976 discloses a process for the production of branched carboxylic acids, which comprises olefins at a temperature of 200-500 ° C. and a pressure of 200-700 bar in the presence of a catalyst, zeolith. By catalytic conversion with carbon oxide and water.
Furthermore, a pentasil-type zeolite is used as a catalyst. According to the illustrated embodiment, only high temperatures (300 ° C.) and pressures (300-500 bar) are used.
It is understood that the disclosed reaction conditions are a source of high operating costs due to necessary safety and environmental measures.
Therefore, there is still a strong demand for further improvements in the process for producing branched carboxylic acids starting from branched olefins and carbon monoxide.
The object of the present invention is an improved process for the production of branched carboxylic acids, on the one hand using relatively mild conditions and on the other hand a process which exhibits high conversion and high selectivity for branched acids. Is to provide. As a result of extensive research and experimentation, an improved method for this purpose was unexpectedly discovered.
Therefore, the present invention provides a method for producing a branched carboxylic acid from a branched olefin by a reaction using carbon monoxide and a solid acid catalyst, and reacting the branched olefin or a precursor thereof in a continuous backmixed reactor. Where sufficient feed components and product agitation to obtain efficient backmixing with continuously fed carbon monoxide and water, branched carboxylic acid, non-converted olefin, monoxide Presence of an acidic ion exchanger having sufficient acid groups to provide the hydrogen necessary to convert the olefin or precursor thereof and carbon monoxide to a branched carboxylic acid while extracting an effluent containing carbon and water. The present invention relates to the above manufacturing method.
In particular, the present invention provides a formula
To an improved process for the preparation of trialkylacetic acids.
The total number of carbon atoms in the trialkyl acetic acid, more preferably 5 to 19, more preferably in the range of 5 to 14, derived from the C 4 -C 14 olefins.
As used throughout this specification, the term “branched olefin or precursor thereof” refers to, in addition to the branched olefin itself, alcohols, esters or ethers that can easily lead to the specific olefin. It means that it can be used as a material, which makes the method more flexible than prior art methods.
In general, all olefins or precursors thereof containing at least one tertiary carbon atom can be converted by this process.
Suitable examples of the continuous backmixing reactor described above are a continuous stirred tank reactor (CTSTR), a fluidized bed reactor or a recycle reactor.
The type of reaction described above is known, for example, from Chemical Reaction Engineering 2nd edition, O Levenspiel.
A continuous stirred tank reactor or a recycle reactor is a preferred reactor.
An important advantage of the process of the present invention is that it exhibits an improved combination of high conversion and high selectivity with respect to the desired branched carboxylic acid compared to prior art processes and is operated at relatively mild conditions. That is.
The catalyst used for the process of the present invention is a solid acidic ion exchanger and exhibits a sufficient amount of acid active sites per volume unit catalyst and the strong acid activity of each acid site.
The catalyst can be selected from the group consisting of resins having sulfonic acid, phosphoric acid or trihaloacetic acid groups.
Preferably, a sulfonated resin is used. More preferably, a sulfonated resin is used in which the resin is a copolymer of styrene and divinylbenzene, a phenol-based resin, a poly (tetrafluoroethylene) polymer or a siloxane polymer.
In a preferred catalyst having active sulfonic acid groups, the resin is an acid strength equivalent to a sulfonic acid cation exchange resin capable of providing sufficient hydrogen, ie, at least 65 wt% sulfuric acid per active site, preferably at least 70 wt% sulfuric acid. It is processed to give a resin having
Preference is given to catalytic solid resins which contain sulfonic acid groups and are derived from copolymers from styrene, divinylbenzene and phenol, or from (tetrafluoroethylene) polymers or siloxane polymers.
More preferred are catalysts derived from styrene and divinylbenzene and having a sulfone group density of> 2 meq / ml dry resin, preferably> 3 meq / ml dry resin, and the copolymer has a divinylbenzene content of 4 to 4 30% by weight, preferably 8 to 18% by weight.
More preferred specific examples of commercially available effective catalysts are AMBERLYST 36 or 38, NAFION or DELOXAN catalysts (AMBERLYST 36 or 38, NAFION and DELOXAN are trademarks).
Most preferred are AMBERLYST 36 or 38, NAFION type catalysts. The reaction temperature of CSTR is in the range of 25 ° C to 200 ° C, preferably in the range of 100 ° C to 150 ° C.
The reactor pressure is in the range of 10 to 200 bar, preferably 50 to 100 bar.
During the reaction, an inert organic solvent that does not interfere with the desired reaction, preferably a solvent that can be easily separated from the other reaction mixture components and can be recycled can be used. As the organic solvent, nonpolar ones can be used in the same manner as polar solvents such as ketones, ethers, substituted aromatics, esters and carboxylic acids.
According to a more preferred embodiment of the production method, the primarily produced branched acid is present as a solvent in the reactor and from there water, CO, to maintain a constant liquid level in the reactor. It is constantly discharged with non-converted olefins and by-products.
According to one preferred embodiment, the CSTR is filled with solvent and catalyst with a solvent / catalyst weight ratio of 0.1 to 0.5 w / w, preferably 0.2 to 0.3 w / w. Each component is continuously introduced into the reactor and the reaction mixture is continuously discharged.
The starting olefin feed is in the range of 0.01 to 10 g / g / hr, the water / olefin molar ratio is in the range of 0.5 to 2 mol / mol, preferably about 1, and CO 2. / Olefin molar ratio is in the range of 0.5 to 1000 mol / mol, preferably 1 to 100.
When using an amount of water that is significantly below the amount specified above, the process becomes less attractive due to low selectivity and uses a stoichiometric (water: olefin = 1: 1) feed. It is sometimes understood that selectivity and conversion are surprisingly improved.
The invention will be further described in the following examples, which are not intended to limit the scope of these specific embodiments.
Example 1
56 g of dry AMBERLYST 15 was charged into a 300 mL CSTR reactor, suspended in 145 mL of n-hexanoic acid (solvent) and brought to 155 ° C. under constant gas purge under 10 bar CO. Activation was achieved by warming, followed by 1 hour at 155 ° C. under 80 bar CO flow (50 g / hr). A feed containing propylene trimer, water and CO (water: trimer molar ratio is 1: 1) is then added to the reactor at 8.5, 1. At 2 and 50 g / h (WHSV 0.15, 0.021 and 0.9 g / g / h), the reactor liquid level was kept constant by removing excess liquid product.
Under these conditions, the reaction proceeded for approximately 24 hours with 75-85% conversion and 93-95% selectivity to branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Comparative Example 1
20 g of AMBERLYST 15 is charged into a stirred batch reactor, dried under vacuum at 100 ° C. for 2 hours and suspended in a solution of 50 g propanoic acid (solvent), 6 g propylene trimer 3 and 0.8 g water. And finally heated to 150 ° C. under 80 bar CO for 65 hr.
Under these conditions, the reaction proceeded with 91% conversion and 8% selectivity over a branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Example 2
In the same manner as described in Example 1, NAFION NR 50 catalyst (59 g) dissolved in 120 mL of hexanoic acid was used and the propylene trimer contained 10 carbon atoms with CO and water under the following conditions: Conversion to branched carboxylic acid.
Propylene trimer 8.8 g / h (WHSV = 0.16 g / g / h)
Water 1.2 g / h (WHSV = 0.021 g / g / h)
CO 52 g / h (WHSV = 0.9 g / g / h)
Temperature 155 ° C
The pressure 80 bar conversion was 88 mol% and the selectivity was 91 mol%.
Example 3
13.6 g of dried AMBERLYST 38 is placed in a 240 mL stirred autoclave, dried under vacuum at 150 ° C. for 2 hr, cooled to room temperature, suspended in 74 g of pivalic acid (solvent) and pressurized under 70 bar CO. Then, the temperature was raised to a reaction temperature of 150 ° C. During the heating period, 23.4 g DIBC (di-isobutyl-carbinol) was slowly and continuously introduced into the autoclave over 17 hours. At the end of the run, the reactor was cooled and removed for analysis.
Under these conditions, the reaction proceeded with 100% conversion and ˜56% selectivity over a branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Comparative Example 2
Example 1 was run, except that 20.4 g DIBC was added to the stirred reactor all at once (ie, batch) and then pressurized to 70 bar CO and the temperature was raised to 150 ° C. The reaction was run again for 17 hours.
Under these conditions, the reaction proceeded with about 100% conversion and ˜13% selectivity over a branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Example 4
Example 1 was now run using AMBERLYST 36 as the catalyst. The amount of catalyst, feed and solvent was about 4 times smaller, ie 3.1, 7.4 and 19 g, respectively.
Under these conditions, the reaction proceeded with ~ 85% conversion and ~ 32% selectivity over a branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Comparative Example 3
Comparative Example 2 was run as a batch process with 4 volumes of catalyst, feed and solvent, ie 12.1, 20.3 and 79 g, respectively. However, the feed was added all at once before the reactor was pressurized to 70 bar CO and the temperature was raised to 150 ° C.
Under these conditions, the reaction proceeded with ˜93% conversion and ˜2.7% selectivity over a branched carboxylic acid having 10 carbon atoms (VERSATIC acid 10).
Claims (10)
のトリアルキル酢酸を製造することを特徴とする、請求項１〜３のいずれか一項に記載の方法。formula
A process according to any one of claims 1 to 3, characterized in that it produces a trialkylacetic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97200537.5 | 1997-02-25 | ||
| EP97200537 | 1997-02-25 | ||
| PCT/EP1998/001128 WO1998038149A1 (en) | 1997-02-25 | 1998-02-24 | Process for the manufacture of carboxylic acids |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2001513099A JP2001513099A (en) | 2001-08-28 |
| JP2001513099A5 JP2001513099A5 (en) | 2005-10-06 |
| JP4025373B2 true JP4025373B2 (en) | 2007-12-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP53732398A Expired - Fee Related JP4025373B2 (en) | 1997-02-25 | 1998-02-24 | Method for producing carboxylic acid |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0968166B1 (en) |
| JP (1) | JP4025373B2 (en) |
| KR (1) | KR100497943B1 (en) |
| AT (1) | ATE219043T1 (en) |
| AU (1) | AU726899B2 (en) |
| CA (1) | CA2282350A1 (en) |
| DE (1) | DE69805980T2 (en) |
| NZ (1) | NZ336802A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW491834B (en) * | 1998-09-21 | 2002-06-21 | Shell Int Research | Process for the manufacture of quaternary carboxylic acids |
| WO2000024700A1 (en) * | 1998-10-22 | 2000-05-04 | Resolution Research Nederland B.V. | PROCESS FOR THE MANUFACTURE OF α,α-BRANCHED CARBOXYLIC ACIDS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3620581A1 (en) * | 1986-06-19 | 1987-12-23 | Basf Ag | METHOD FOR THE PRODUCTION OF CARBONIC ACIDS |
| US5250726A (en) * | 1992-08-24 | 1993-10-05 | E. I. Du Pont De Nemours And Company | Process for the preparation of 3-pentenoic acid from butadiene |
| JPH10511666A (en) * | 1994-12-28 | 1998-11-10 | エクソン・ケミカル・パテンツ・インク | Production of trialkylacetic acid using solid cationic resin catalyst system |
-
1998
- 1998-02-24 JP JP53732398A patent/JP4025373B2/en not_active Expired - Fee Related
- 1998-02-24 AU AU64001/98A patent/AU726899B2/en not_active Ceased
- 1998-02-24 KR KR10-1999-7007721A patent/KR100497943B1/en not_active IP Right Cessation
- 1998-02-24 CA CA002282350A patent/CA2282350A1/en not_active Abandoned
- 1998-02-24 DE DE69805980T patent/DE69805980T2/en not_active Expired - Lifetime
- 1998-02-24 AT AT98909484T patent/ATE219043T1/en not_active IP Right Cessation
- 1998-02-24 NZ NZ336802A patent/NZ336802A/en unknown
- 1998-02-24 EP EP98909484A patent/EP0968166B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69805980T2 (en) | 2003-01-23 |
| KR100497943B1 (en) | 2005-07-01 |
| ATE219043T1 (en) | 2002-06-15 |
| AU726899B2 (en) | 2000-11-23 |
| EP0968166A1 (en) | 2000-01-05 |
| KR20000075656A (en) | 2000-12-26 |
| JP2001513099A (en) | 2001-08-28 |
| AU6400198A (en) | 1998-09-18 |
| DE69805980D1 (en) | 2002-07-18 |
| NZ336802A (en) | 2000-09-29 |
| EP0968166B1 (en) | 2002-06-12 |
| CA2282350A1 (en) | 1998-09-03 |
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